High temperature negative temperature coefficient thermistor material and preparation method thereof

Field of the Present Invention

The invention belongs to the field of temperature sensing technique, more particularly relates to a composite thermal thermistor material and a preparation method thereof, in which the prepared thermal thermistor material can be used for a temperature sensing technique.

The negative temperature coefficient (NTC) thermistor is widely used in different kinds of circuit system as a compensate device, whose resistance decrease with the temperature rising up. Compare with the traditional temperature sensing element such as thermocouple, thermal resistance, the main characteristic of NTC thermistor is their high sensibility and low cost. The high temperature NTC thermistor is more stable than normal NTC thermistor, so it can be used for temperature of 1000° C., which makes it a better choice as temperature sensing element in high temperature automobile applications.

The main parameters of NTC is the resistivity and their negative temperature coefficient B, which was used to evaluate the relation between resistivity and temperature. In order to realize the temperature detection range from 0° C. to 1000° C., it is important for the NTC thermistor to simultaneously possess high resistivity and low B value. However, too high B value will lead to less resistivity in high temperature but too low B value will influence the sensitivity. Usually, the range of B value for high temperature NTC is 2000˜4000, and it is difficult to tune the B value for a given system. Thus, there is urgent need to develop a method to tune the B value for NTC materials.

In view of the above-described problems, the present invention provides a composite NTC material and a preparation method thereof, which can achieve the tunable B value to fabricate high temperature NTC thermistor by synthesis two different kinds of materials. Meanwhile, the NTC thermistor can effectively used with B value from 2000˜4000, with the good performance of long-term stability and NTC effect.

In order to achieve the above objective, according to an aspect of the present invention, there is provided a composite NTC thermistor material, wherein the NTC thermistor material is formed by oxides of pyrochlorite and perovskite. The ratio of two materials is (70:30)˜(90:10), the main elements in oxide of pyrochlorite are calcium, titanium, tungsten and cerium. Correspondingly, the main elements in oxide of perovskite is yttrium, manganese and chromium.

Further, the perovskite oxide and the pyrochlorite oxide are YCr 0.5 Mn 0.5 O 3 and CaWO 4 —CeTi 2 O 6 , respectively.

Further, the molar ratio of yttrium manganese and chromium in the perovskite structure oxide is (2˜2.5):(0.8˜1.2):(0.8˜1.2). The molar ratio of calcium, titanium, tungsten and cerium in the calcined chlorite oxide is (0.8˜1.2):(0.8˜1.2):(0.8˜1.2):(2˜2.5).

For example, the molar ratio of yttrium manganese and chromium in perovskite oxides is 2:1:1, and the molar mass ratio of calcium, titanium, tungsten and cerium in the calcined chlorite oxide is 1:1:1:2. The optimum resistivity and B value of the prepared composite thermistors can be achieved by using the molar mass ratio. The properties of the prepared composite thermistors are superior.

According to another aspect of the present invention, there is provided a preparation method of a composite NTC material, comprising:

(1) The analytical pure Y 2 O 3 , Mn 2 O 3 and Cr 2 O 3 are mixed grinding, and the molar ratio of the three is 2:1:1, then calcined the mixture at 1200° C. for 1-2 hours to obtain the YCr 0.5 Mn 0.5 O 3 oxide powder;

(2) The analytical pure CaCO 3 , CeO 2 , TiO 2 and WO 3 were mixed to grind, and the molar ratio of the four was 2:2:2:1, and then calcined the dried powder at 1000° C. for 3 h to obtain the CaWO 4 —CeTi 2 O 6 oxide powder;

(3) The perovskite oxide YCr 0.5 Mn 0.5 O 3 powder was prepared and the PVA binder was added to the perovskite oxide powder to disperse the perovskite oxide powder evenly, and the uniformly dispersed particles were sintered directly at 1400-1600° C. for 1-2 h.

(4) Taking step (3) perovskite oxide YCr 0.5 Mn 0.5 O 3 powder after sintering, and preparing calcined chlorite oxide CaWO 4 —CeTi 2 O 6 powder in step (2), grinding them uniformly for 4-8 h. The molar ratio of perovskite oxide YCr 0.5 Mn 0.5 O 3 powder to calcined chlorite oxide CaWO 4 —CeTi 2 O 6 powder is (70:30)˜(90:10);

(5) Mixing and grinding the uniform powder in step (4) and adding the PVA binder to form the uniformly dispersed granular particles again, and then forming the uniformly dispersed particles into a wafer after the mold molding;

(6) The formed wafer is sintered at 1400° C. to form a B value adjustable thermistor material;

(7) The platinum paste is coated on the surface of the sintered thermistor material in step (6) and then kept at 1200° C. for 2 h;

(8) The thermistor material obtained in step (7) is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip.

The invention also discloses an application of a composite thermistor material. The composite thermistor material is used to prepare a composite thermistor. The platinum wire was bonded to the two ends of the thermistor chip after cutting, and the high temperature thermistor with lead was formed after high temperature treatment at 1200° C.

The invention also discloses an application of a composite thermistor material. The composite thermistor material is used to prepare a high temperature dense ceramic thermistor temperature sensor.

Beneficial effect: the composite thermistor material in the invention, according to the ratio of its composite material, the obtained thermistor coefficient B value is different, which can be adjusted by the B value of 2000-4000 to meet the requirements of different industrial production. The invention can be widely used in the field of automobile exhaust gas measurement and various temperature measurement, and is a low price and stable thermistor material.

FIG. 1 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

FIG. 2 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

FIG. 3 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

FIG. 4 is a schematic diagram of the resistance and temperature characteristic curve in embodiment 1;

For clear understanding of the objectives, features and advantages of the present invention, detailed description of the present invention will be given below in conjunction with accompanying drawings and specific embodiments. It should be noted that the embodiments described herein are only meant to explain the present invention, and not to limit the scope of the present invention.

The composite NTC thermistor material in the present invention is formed by perovskite structure oxide and pyrochlorite structure oxide. The molar ratio of the two materials is (70:30)˜(90:10), and the perovskite structure oxide contains yttrium, manganese and chromium. The pyrochlorite oxide containing calcium, titanium, tungsten and cerium. Among them, perovskite oxide and pyrochlorite oxide are YCr 0.5 Mn 0.5 O 3 and CaWO 4 —CeTi 2 O 6 , respectively. The molar ratio of yttrium, manganese and chromium in perovskite oxide is 2:1:1, and the molar ratio of calcium, titanium, tungsten and cerium in calcined chlorite oxide is 1:1:1:2. The composite NTC thermistor material can be prepared according the following steps:

(1) The analytical pure Y 2 O 3 , Mn 2 O 3 and Cr 2 O 3 are mixed grinding, and the molar ratio of the three is 2:1:1, then calcined the mixture at 1200° C. for 1-2 hours to obtain the YCr 0.5 Mn 0.5 O 3 oxide powder;

(2) The analytical pure CaCO 3 , CeO 2 , TiO 2 and WO 3 were mixed to grind, and the molar ratio of the four was 2:2:2:1, and then calcined the dried powder at 1000° C. for 3 h to obtain the CaWO 4 —CeTi 2 O 6 oxide powder;

(3) The perovskite oxide YCr 0.5 Mn 0.5 O 3 powder was prepared and the PVA binder was added to the perovskite oxide powder to disperse the perovskite oxide powder evenly, and the uniformly dispersed particles were sintered directly at 1400-1600° C. for 1-2 h.

(4) Taking step (3) perovskite oxide YCr 0.5 Mn 0.5 O 3 powder after sintering, and preparing calcined chlorite oxide CaWO 4 —CeTi 2 O 6 powder in step (2), grinding them uniformly for 4-8 h. The molar ratio of perovskite oxide YCr 0.5 Mn 0.5 O 3 powder to calcined chlorite oxide CaWO 4 —CeTi 2 O 6 powder is (70:30)˜(90:10);

(5) Mixing and grinding the uniform powder in step (4) and adding the PVA binder to form the uniformly dispersed granular particles again, and then forming the uniformly dispersed particles into a wafer after the mold molding;

(6) The formed wafer is sintered at 1400° C. to form a B value adjustable thermistor material;

(7) The platinum paste is coated on the surface of the sintered thermistor material in step (6) and then kept at 1200° C. for 2 h;

(8) The thermistor material obtained in step (7) is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip.

The composite thermistor material is used to prepare a composite thermistor. The platinum wire was bonded to the two ends of the thermistor chip after cutting, and the high temperature thermistor with lead was formed after high temperature treatment at 1200° C.

The composite thermistor material can also be used to fabricate high temperature dense ceramic thermistor temperature sensor.

A, preparing the composite NTC thermistor material, which specifically includes the following steps:

a, the prepared perovskite oxide YCr 0.5 Mn 0.5 O 3 , and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600° C. for 1-2 h;

b, after sintering, perovskite oxide YCr 0.5 Mn 0.5 O 3 powder was obtained and mixed with the prepared CaWO 4 —CeTi 2 O 6 powder for 4-8 h at the molar ratio of 70:30;

c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200° C.;

f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

g, the resistivity at room temperature (25° C.) is 2540 (k Ω*cm), the resistivity at high temperature (900° C.) 0.0076 (k Ω*cm), B value (25-200) is 4378, B value (200-800) is 4797, the temperature resistance curve is shown in FIG. 1 ;

B, preparing the composite NTC thermistor material, which specifically includes the following steps:

a, the prepared perovskite oxide YCr 0.5 Mn 0.5 O 3 , and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600° C. for 1-2 h;

b, after sintering, perovskite oxide YCr 0.5 Mn 0.5 O 3 powder was obtained and mixed with the prepared CaWO 4 —CeTi 2 O 6 powder for 4-8 h at the molar ratio of 80:20;

c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200° C.;

f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

g, the resistivity at room temperature (25° C.) is 151.62 (k Ω*cm), the resistivity at high temperature (900° C.) 0.0048 (k Ω*cm), B value (25-200) is 3798, B value (200-800) is 4370, the temperature resistance curve is shown in FIG. 2 ;

C, preparing the composite NTC thermistor material, which specifically includes the following steps:

a, the prepared perovskite oxide YCr 0.5 Mn 0.5 O 3 , and PVA binder are added to disperse the raw powder into granular form, then the uniformly dispersed powder is sintered at 1400-1600° C. for 1-2 h;

b, after sintering, perovskite oxide YCr 0.5 Mn 0.5 O 3 powder was obtained and mixed with the prepared CaWO 4 —CeTi 2 O 6 powder for 4-8 h at the molar ratio of 90:10;

c, the uniform powder was added to the binder to form the granular uniform dispersed powder again, and then formed the disk after the mould forming;

d, the formed disk was sintered at 1400-1500 temperature to form a B value adjustable thermistor material;

e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200° C.;

f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

g, the resistivity at room temperature (25° C.) is 30 (k Ω*cm), the resistivity at high temperature (900° C.) 0.0022 (k Ω*cm), B value (25-200) is 3263, B value (200-800) is 4135, the temperature resistance curve is shown in FIG. 3 ;

D, preparing the composite NTC thermistor material, which specifically includes the following steps:

a, the analytical pure Y 2 O 3 Mn 2 O 3 Cr 2 O 3 was mixed with the molar ratio of 2:1:1 and then calcined at 1200° C. for 1-2 h to obtain the YCr 0.5 Mn 0.5 O 3 oxide powder.

b, the powder obtained in step a is dried and added with binder to disperse the particles evenly, and the disk is formed by mould forming process.

d, the formed disk was sintered at 1400-1500 temperature to form a thermistor material;

e, the platinum paste was coated on the surface of the sintered thermistor material and kept for 2 h at 1200° C.;

f, the platinum coated thermistor material is cut according to the requirement, and the platinum lead is welded to the cut thermistor chip;

g, the resistivity at room temperature (25° C.) is 21.54 (k Ω*cm), the resistivity at high temperature (800° C.) 0.01864 (k Ω*cm), B value (25-200) is 2881, B value (200-800) is 3083, the temperature resistance curve is shown in FIG. 4 .